Abstract
Marcus theory calculations of rates of electron transfer (ET) have been carried out for attack by NO+ and NO2+ on various reactive aromatic substrates including alkylbenzenes and naphthalene. While reasonable agreement between calculation and experiment is obtained for nitrous acid catalysed nitration, the calculated rate of electron transfer in the nitration of naphthalene by nitronium ion is too low by between nine and fifteen orders of magnitude. Possible reasons for this discrepancy are discussed and it is suggested that H2NO3+ may be the ET agent responsible for the previously observed CIDNP effects in this system. Semi-empirical molecular orbital calculations have been carried out on relevant species, including reaction coordinates for the nitration of naphthalene in the 1- and 2-positions. Transition state energies suggest that attack in the 1-position is very much favoured by the ET process.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callMore From: Journal of the Chemical Society, Perkin Transactions 2
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
